Molding of resin dispersions



May 19, 1953 A. A. RooT MOLDING oF RESIN4 DISPERSIONS Filed sept. 8, 1949 nvenzor Andrew A Raaf Patented May 19, 1953 UN ITEDL MOLDING '0E RESIN DISPERSION S Andrew A. Root, ySalem, Ma'ss l,aassignor -to United --f SheMachineryCrporation; Flemington-N. J a corpnrationfoff-N ew J ersey Application September 8, 1949;Serial No."114\,630

6 Claims;

, 1 i' This 'invention relates toJ a method for molding a bodyofplastic ori-thesurlaceiofan articlefand particularly y to an improved-method of forming a soleona shoe.

, Ithas vbeen proposedrto'dmold a Vsole fon the bottomf of" a shoe -by a method involvingz'placlng biscuitsuw or preformsef unvulcanizedrubber* in a mold* andpressingthe shoe-firmly against' the upperface-:of the mold to vforrrra molding cham ber.W The mold and rubberwereheatedandthe rubber material *wa/sf conformed-to the shape of the-mold;- bonded -tovv 'the-bottom ofy the shoe and vulcan-ized;v 2

'Ili'e`k 4vulcanizatiorrof -'a soleonf-an upper -involves' ynumerous 'Y technical=- dinic'ulties-v` and 'economic disadvantages; 'andfin :mycop-ending applicatiohrSeral'NojJSS, ledf Octollerl 27; L1948', I have ldisclosed` a pressure-lessv method for molding a plastic, wear-resistant sole on a shoe which avoid'smanyofthe-difhcult-iesi-presentin the' vulcanizationmethod`r offsole#molding` In* that method there is conned between the bottom'of an"article-offootwear; 7'such as-a 'shoeg' and a molding-surface;a Vboly'oi'a fluid dispersion of resin :particles-Ain a liquid -plasticizer'havingno substantial -solv'ent actionon` the resin; When cool; This fluid--dispersion-isthen caus'edto set"upf-to a iirmresili'ent condition which 'it reproduces the -moldingsurface'andis -rinly bonded" to the bottom'mfrtheshoe` by Vheating it 'to eifect'at least partial solution ofthe'resin andA plasticizer. This method givesy excellent results; but it requires a substantial period"'ofheating of the resin dispersionl inthe moldso thatzforthe manufacture of a substantial numberof-s'hoesa large number of 'molds'iwi'll loe-required# Itfi's `a feature offthe present' invention topro' vide animproved method forV molding a Wear*- resistant -soleon-a shoe whereby thetimer during whichA the' shoe and mold aremaintainedin rcooperative relationfis substantially reduced.-

Inaccordance: lwith the presenti invention 'a shaped body oi-A plastic vis `formed on 4the surface ofan article by confining between "the 'surface of the article-and'v a moldingsurface a body of fluid pastedisp'erslon-of'resiniparticles in a liquid plasticizer having 'no lsubstantial solvent action on the resin-when cool but'capableo-at'least partly dissolving the resin 'When-:heated: Heat is supplied throughK the-molding surface-'to con` vertportions ofJ-the Afluid dispersion adj acent` it to a hrm resilient `condition'reproducing the configuration 'of theA molding surface and adhering rmly toi-'the artic-le to-providea shape-retain` ing shel1conningthe' L-unsolidifled Aportion' of-l the 2A, dispersion against the vsurface of the article;k `The article? and' adhering 'shell with fluid fresindisrpersion therein are :removed from' engagement withthe' molding surface, and the remaining fluid resin dispersion is `solidified 'by further: applicar-v tion off hat'faway from-contact `with the'molding surface. If desired, the surface' of' theasolidiiied resinwhile in softened' condition from thefurther heating or vfrom a reheating'frnay' be'formedfiurtherbyv pressin'gvit lightly with'a shapedrsurface'.

The inventionwillbe' further described'inrcon'Y nectionwith thev accompanyingdrawings-'forming partI othepresent disclosure; Inthe drawings, Fig; 'l is a sectionalelevation-ot` a shoermounted 'on a lastand held; infcooperative relationship with Ta heated 4inold'xhy'a pIBSS l Fig. 2 ista -sectionalil elevation ofi a Ashoe! ona last-with va solidified resinshell Tandv unsolidied resinl Within fthe' shell on the i bottom ofi the felice, and ,hea'tllarnpsi disposed :to-heat 'the soledurther; :andv

FigpfS is a perspective offra shoe fmounte'ol 'on-a last and of a shaped surface Abeing :appliedto' the sole l of -the' shoe" to A produce ra 'desired configuration on the sole of the shoe.

In practicing the" metho'dfof the'present ini/entiongianxartielesuch asra shoe lylisiprepared andmountedonia suitable formrsu'ol'ilafsfa -last t2 'which zwill `retain4 it `inshaped condition Afor molding vof Ja solefth'ere'on The Vvshoe -Hl illus# trated ini the figures is a conventional stitohdown shoe'rhaving aninsole' Hlbut not havinga foonventionall uter'solesf The lower edges: -16' f the shoe-are' 'flared :outward and y'staple :or thiiea'd lasted tothe'insole 14N Welting l8 is applied' to the'fla'rededges It of the upper, andthelwelti'ng I8,E flared edges it; and insole ill "are stitched together tol-provide a a'nge' 2li;

The-bottom of the shoe lli; in thi's'casa-the rbottom `of= the -insolefflL rnayf then be coated'inr lightly? impregnated Withv a thihlyluid, 'resinous material, suitably a resin latex. A suitable resin latex is a vtlfli% 'solids polyvinyl chloridelatex. Other 'y aqueous dispersions or flatices of resins 'compatible-'with the resin to be molded nthe shoel may'beused.- When the bottom surfaceof the shoe has been treated'with'the reslnous materialfit tis'driecl 'if vnecessary and -is then ready forthe molding'operation. This coating 0r impregnating treatment improves the vhond between the shoe' and a sole moldedjthereon but may be omitted.'

An' apparatus adapted for forming a sole on a 4shoe having a flange or Welt around its bottom `edge-is illustrated in Fig. v1 and comprises a heated surface 22, a heat conducting mold 24 thereon, and an articulated retaining ring 28 supported by a frame 28 which is connected to the transverse beam 30 of a press. The mold 212 comprises a block of metal having a flat bottom so that it is heated efficiently by the heated surface and having a shaped recess 82 therein, the shape of the recess corresponding to the shape of the shoe sole 34 which it is to form. The bottom surface 36 of the recess may be plain or may be -shaped at its forward portion to form a desired sole pattern on material molded therein. The rear portion 38 of the recess is depressed below the general level of the forward portion for molding a heel portion 40 integral with the sole. The surface of the rear portion may also, if desired, be formed to provide a desired tread pattern on the tread portion of the heel. The sides 42 of the recess 32 extend up from the bottom surface 36 for a distance corresponding to the desired thickness of the sole 34 to be molded. Soles of any desired thickness ranging from as little as 33-2 up to any desired value may be molded by the method of the present invention. The term substantial thickness is used herein to describe soles within this range.

The shoe l5 mounted on a last l2 is disposed within the pressure ring 26 with the edges of the ring against the flange 20 around the edge of the shoe. The ring 28 is then pressed down to force the flange 20 into sealing engagement with the upper surface 44 of the mold in alinement with the recess of the mold. Fluid or pasty resin dispersion is introduced into the space defined by the bottom of the shoe upper, i. e., bottom of the insole I4, and the mold surfaces through a conduit 46 which is illustrated as being disposed in the heel portion 48 of the mold. The resin dispersion is supplied until the mold is completely filled as evidenced by escape of resin from the narrow groove 48 in the toe portion of the upper surface i 44 of the mold. The supply of dispersion is then cut oi and the closure slide 50 is forced across the opening at the end of the conduit 48 by the spring 52 to prevent loss of dispersion frornthe mold.

The assembly of shoe and heated mold containing the resin `dispersion is permitted to stand for a period suicient to solidify those portions lof the resin dispersion adjacent the mold to a thickness such that it forms a shape-retaining shell.

vplaced bottom upward on a conveyor 55 and moved beneath a bank of infra-red lamps 58 disposed to apply heat to the shell 54 as the shoe is carried along. The remaining portions of the resin dispersion within the shell are solidied by the subjection to the infra-red heating for a period of from four to twelve minutes and form vwith the shell a uniform, homogeneous resin sole 34 firmly adhering to the bottom of the shoe.

Resin dieper-sions employed in the method and article of the present invention are liquid to pasty mixtures of from 30% to 70% of thermoplastic The Aboundary between the solidified material and the resin particles in from 70% to 30% of a liquid plasticizer having no substantial solvent action on the resin when cool, but capable of combining physically with the resin particles when the dispersion is heated to form a uniform mass of plasticizer resin. The relative proportions of resin and plasticizer selected will depend on the physical properties desired in the nal tread surface. For example, high proportions of plasticizer relative to the proportion of resin will give a softer more rubbery sole than lower relative proportions within the range.

The particle size of the dispersed resin may vary Within relatively wide limits. However, particles of from 275 `to 325 microns have been found very satisfactory.

Resin dispersions which have been found particularly satisfactory in the process of the present invention include: a dispersion of particles of a copolymer of vinyl chloride and vinyl acetate containing from to 88% of vinyl chloride in a substantially equal Vquantity by weight of dioctylphthalate; a dispersion of 50 parts of particles of a vinyl chloride, vinyl acetate copolymer containing 85% to 88% `of vinyl chloride, in 45 parts of dioctyl-phthalate; and a dispersion of 50 parts of a vinyl chloride, vinyl acetate copolymer, and 49 parts of an ester type plasticizer which may be tri-cresyl phosphate, dibutyl phthalate or dioctyl phthalate. Dispersions of other resins, including polymethyl methacrylate and vinyl chloridevinylidene chloride copolymers in plasticizers in which they are not substantially soluble in cold condition and in which -they are dissolved or gelled when heated, may be employed, provided the resin body obtained on heating the resin dispersion possesses the toughness, hardness and resilience to render it suitablel for its intended use.

It has been found desirable in dispersione of the type employed to use about 1% of a conventional stabilizer.

Limited amounts of fillers may be incorporated in the dispersion prior to molding. Fillers which have been employed include bers of copolymerized vinyl chloride and vinyl acetate, sisal fiber, diatomaceous earth and clay. Other fillers may be used. The percentage of llers will depend on the stiffness, strength, or other propertydesired and may be as much as 50% on a volume basis, preferably about 25%.

The dispersion may also include any compatible dye or pigment or combination of these. Where pigment is used it may rst be ground into the plasticizer.

With a resin dispersion comprising a copolymer of vinyl chloride and vinyl acetate containing from 85% to 88% of vinyl chloride in a substantially equal quantity .by weight of dioetylphthalate and using a mold temperature of 270 to 325 C., a shape-retaining shell of solidified dispersion adhering firmly to the shoe is formed in a heating period of approximately one minute. With hotter molds, a satisfactory shell may be formed in as little as 40 seconds. Heating periods of greater length than one minute may of course be employed. Longer periods of heating in the molds reduce the number of shoes on which soles can be molded in a given period of time with a given number of molds.

Using infra-red radiation units, for example 875 watt infra-red lamps, spaced at a distance of about 6 to 12 inches from the surface of the soles of shoes carried by the conveyor, and with centers spaced a distance of about 8 to 12 inches apartl'on 1 a rline'l parallel -ztoivthe direction.l of the conveyonait iis found th'atithe :.further .or secondary'heatingiperi'od may :beffromxfi to .112' minutes torform a sole *.surface which is fsoli'dthroughont and'l firmly adherent` to' the i shoe;y

Asan' alternative tothe infraared lampjheat'- ing treatment Y'for the' further" or. `secondary heating fof ithe'; shoes, other' types `of :heating .such as oven aheating or:.;the actionxcf a high-free quency electric field on the dispersion, maythe' employed` to provide thev heat knecessary tolsolidfy .the r :fluid "portions .of .theA dispensionl :1 LIn :a high-frequency electric field. M1800 volts Land .a frequency of. from .20 5110140 mega-cycles .created between. electrodes disposed at .opposite .edgeswof the soles 'satisfactory heating `may ,he obtained in! ras .short :a period as 30 second-sto 2 minutes; For loven heating.. the .entire assembly of fshoe and/shell with 'unsolidiiied' dispersioiifinayz be placedfin an oven` atfa trmperature.'from''lnf F. to;3'7,5-F. for a period of rfrom toozminutesxto cause the remainder ofthe dispersion tosolidifyi The bottom surface. of i the .molded .sole :in heated. condition as itScomes frornzthe step of solidifying the-dispersion 'within the'y she1l;...or from. a rehea-ting if the sole hasbeen permitted to cool after 'solidication may be furtherorined by' a suitable contoured surface;Y Aslillustrated inl Fig; .13, this surface-:maybe a noted rolled which isrolledl with lightipressure, e. pres- 5 sure such asrnayreasily be applied bysa workman moving the Irollercverthe surface of the. sole. The surface. of the sole is given :a surface com tour.v such asl the: transverse lcorrugations .Sil

complementary to the-contour of tl'reroll.v This ture of Widelyvaried type'sofshes. Thusfysoles u and/or heels ,may be" moldedon shoes ofany type includingwelt,V stitchdoivn, McKay, pre-vvelt, slip lasted, Littleway 'or -otherfshce construction, and

maybewformed on fabricfootwear such asfslipv-i pers or even on socks.;` Thearesin dispersion is fluid and enters readily into al1 portions of even the most complicated mold designs. .also the pressureless character of the molding operation simplies operating procedure as well as mold design so that many variations may be introduced into the process. For example, mechanical inserts may be employed without complicated arrangements for retaining them in position as might be required in pressure molding operations.

I-Iaving thus described my invention, what I claim as new and desire to secure by Letters Patent of the United States is:

1. The method of providing a molded member of substantial thickness on a surface of an article which comprises bringing together the article and a molding surface to provide between the surface of the article and the molding surface a confined space of substantial thickness, supplying to the space a body of a fluid paste dispersion .cfa-'resin rparticles,risupplyng :heatatc: said body.' through Ysaidr'no'ldingzsurface; maintaining the' article andi dispersion'. contactfwith; said molding -surfacefto'"solidify ther-portion- 'ofthe dispersion"adjacentathev molding surface" tota depth such that it forms a shape-retainingfshell confining .the .unsolidiiiedv portion". .of `lthe' dispersionzagfainst 'the zsurfa'ce yof the article. andi-the solidiedimateri'a'l Vof 'the 'shell bonds .itself firmly tothe portions lof. the .article .adjacent :the mold-f ing surface; removing-the article together with' the'.adheringlzsolidied shell and unsolidifiedi dis persion. within the shell fromnengagement with' the-melding surface, and subjecting the. shell andnfluid paste :dispersion therein 'torfurther 'heat to convert the remainder. of the.` uid dispersion to a .solid .resilient condition firmlyv bonded to' thev article,r .saidpaste' dispersion L.being a .'-rluid mixture ofrresin particles and liquid.' plasticizer in which the resin .is not dissolved'to'a substan. tial extent whenifcoldbut is vdissolved"when the dispersion is'heated;

2. The method of :providingfa *moldedttread Inemb'erfof substantial thickness on an article' .of footwear which. :comprises bringing ytogether the' articleand a molding surface to provide between the .article and the#molding. surface a confinedV spaceA dening the# shapefwof.v the'v desired tread' member,supplying .tothespace a body of a duid paste dispersion -of resin. particles, supplying. .heat to`^said `4body .through said' .molding wsurface,` maintaining .the articl'eand .dispersion inlicontact 'with said ymolding surfacefto .solidify the por-tienv of thedispersion adjacent thief-molding surface to a depth such that. it lforms'a 'shape` retaining .shell connnling.1unsclidiiiedi-'portions of theidispersionagainst.the surfac'enof the article and ithefsolidied; .material of theshel-l' bonds. itself irmlytc the portions of the articleadija'- cent the molding surface; removing.' thearticle togetheri withiftlre: .adhering .solidified .Shelli .and unsolidied dispersion Within theshell from enf gagement .with the molding. surface, andisufbiecit ing:- theshell*- and' -uid'4 paste dispersion therein to furtherL heat :to convert the .remainder :of the fluid! .dispersion '.to Va .solidresilienta.condition rmlybonded' to thearticle; said paste dispersion beingfa ifluid mixturerfof resintpartiolesand..'a lio-uid plasticizeri-in.which lthe resin is vnotfalls-- sclvedtoi a snbs'tantial; extent Ywhen -rcold but. is dissolved when thedispersionis heated;`

3. Thearnethod of providing'l a Vmoldedtread memb'eriofisubstantialz'thickness on an. article of footwear; Whnhv comprisesrbringingr .togetherl .the anticleanda moldingV surface'toprovide between the article and the molding surface a confined space defining the shape of the desired tread member, supplying to the space a body of a uid paste dispersion of resin particles, supplying heat to said loody through said molding surface, maintaining the article and dispersion in contact with said heated molding surface to convert the portions of the dispersion adjacent the molding surface to a thickness such that it forms a shape-retaining shell conning unsolidified portions of the dispersion against the surface of the article and the solidified material of the shell bonds itself rrnly to the portions of the article adjacent the molding surface, removing the article together With the adhering solidified shell and unsolidiied dispersion within the shell from engagement with the molding surface, and subjecting the shell and fluid paste dispersion therein to heating by radiation to convert the remainder of the fluid dispersion to a solid resilient condition firmly 'bonded 'to the article, said paste dispersion being a fluid mixture of resin particles and a liquid plasticizer in which the resin is not dissolved to a substantial extent when cold but is dissolved when the dispersion is heated.

- 4. The method of providing a molded member of substantial thickness on an article which comprises bringing together the article and a molding surface to provide between the article and the molding surface a confined space of the shape of the desired member, supplying to the space a body of a fluid paste dispersion of resin particles, supplying heat to the molding surface to solidify the portion of the dispersion adjacent the molding surface to a depth such that it forms a shaperetaining shell confining the unsolidifled portion of the dispersion against the surface of the article and the solidified material of the shell bonds itself firmly to portions of the article adjacent the molding surface, removing the article together with the adhering solidified shell and unsolidifled dispersion Within the shell from engagement with the molding surface, subjecting the shell and uid paste dispersion therein to heat to convert the fluid dispersion to a solid resilient condition firmly bonded to the article, and pressing the solidified dispersion While in heated condition against a forming surface to provide a desired surface on the solidified resin dispersion, said paste dispersion being a fluid mixture of resin particles and liquid plasticizer in which'the resin is not dissolved to a substam tial extent when cold but is dissolved when the dispersion is heated.

5. The method of providing a molded tread member of substantial thickness on an article of footwear which comprises bringing together the article and a molding surface to provide between the article and the molding surface a confined space of the shape of the desired tread member, supplying to the space a body of a fluid paste dispersion of resin particles, supplying heat to the molding surface to solidify the portions of the dispersion adjacent the molding surface to a thickness Such that it forms a shape-retaining shell confining the unsolidied portion of the dispersion against the surface of the article and the solidified material of the shell bonds itself firmly to the portions of the article adjacent the molding surface, removing the article together With the adhering solidified shell and unsolidied dispersion Within the shell from engagement with the molding surface, subjecting the shell and fluid paste dispersion therein to heat to convert lthe uid dispersion to a solid resilient'condition firmly bonded to the article, and pressing the solidified dispersion while in heated condition against a forming surface to provide a desired tread surface on the solidified resin dispersion, said paste dispersion being a fluid mixture of resin particles and liquid plasticizer in Which the resin is not dissolved to a substantial extent When cold but is dissolved when the dispersion is heated.

6. The method of providing a molded tread member of substantial thickness on an articleof footwear Which comprises bringing together the article and a molding surface to provide between the article and the molding surface a confined space of the configuration of the desired tread member, supplying to the space a body of a fluid paste dispersion of resin particles, supplying heat to the molding surface to solidify the portion of the dispersion adjacent the molding surface to a thickness such that it forms a shape-retaining shell confining the unsolidified portion of the dispersion against the surface of the article and the solidied material of the shell bonds itself firmly to the portions of the article adjacent the molding surface, removing the article together with the adhering solidified shell and unsolidified dispersion Within the shell from engagement with the molding surface, subjecting the shell and duid paste dispersion therein to heating by radiation to convert the fluid dispersion to a solid resilient condition firmly bonded to the article, and pressing the solidified dispersion While in heated condition against a forming surface to provide a desired tread surface on the solidified resin dispersion, said paste dispersion being a fluid mixture of resin particles and liquid plasticizer in which the resin is not dissolved to a substantial extent when cold but is dissolved when the dispersion is heated.

ANDREW A. ROOT.

References Cited in the le of this patent UNITED STATES PATENTS Number Name Date 255,139 Burr Mar. 21, 1882 1,691,347 Gray Nov. 13, 1928 1,989,853 Finn Feb. 5, 1935 2,032,508 Seiberling Mar. 3, 1936 2,129,106 Szerenyi Sept. 6, 1938 2,470,089 Booth May 17, 1949 FOREIGN PATENTS Number Country Date 500,298 Great Britain Feb. 7, 1939 

